Insecticidal aerosol compositions comprising a 1, 1, 1-trichloro-2, 2-bis (ethoxy methyl phenyl) ethane in a chloro-fluoromethane



Patented May 5, 1953 UNITED STATES 1 PATENT 1 OFFICE INSECTICIDAL AEROSOL COMPOSITIONS COMPRISING A 1,11'TRIGHLOR0*2,2'. BIS (ETHOXY PI'IENYL) ETH ANE IN A CHLORO-ELUOROMETHANE Louis A. Mikeska, Westfie'ld, Ni'j -assignor' to Standard Oil Develop ration of Delaware ment Company, a. corpo- No Drawing. Application April 1, 1950,; v

This invention relates to new and useful improvements in insecticidal compositions, more particularly it relates to an improved insecticide ideally adapted for aerosol dispersion.

Compounds of DDT type (1,1,1 tri-chloro-2,2- di (e-chloro-phenyl) ethane) are known to possess substantial insecticidal activity. These com= pounds have certain disadvantages, e. g., their knockdown strength is not very great, and consequently aerosol formulations of necessity usual-' where either the ethoxy or methyl group is in a. position para to the CI-IC'Gls linkage and the: groupnotin the para position is in an ortho position to thegroup in the para position:

Because of the nature of the reaction when-the ethoxy group tends to occupy the position para to the CHC Ch linkage the methyl group of-neceS- I 3o sity assumes the meta position with respect to the tri-chloroethyl group, and retains its ortho posianalogy applies when the methyl substituent' occupies the para position on the benzene ring. The 14 active ingredients of this invention are thus a mixture of isomers which have in all cases an additional substituent on the benzene ring in addition to the substituent in the 4 or para position. The active ingredients of this invention are thus best characterized as the reaction product of the condensation reaction between chloral hydrate and o-ethoxy toluene. 1

The product of this invention is more soluble than DDT in aliphatic hydrocarbons so that odorous auxiliary solvents are unnecessaryfor aerosol fonnulations. It also has better knockdown characteristics than DDT so that auxiliary" knock-down agents are also unnecessary. These points are important because aerosol formula- Serial No. 153,439 5 Claims. (Cl. 167*30) tions are usually limited to a total of wt. per cent non-volatile materials, which include the m secticide, knock-down agents, auxiliary solvents I and mineral spray oils.'

It is especially surprising to find that the product of this invention is of the same order of insecticidal activity as DDT in view of the fact that it is well known in the art that in DDT type compounds the presence of even one additional substituent on the benzene ring, in addition to the one in the 4 position, causes a diminution of activity. Other compounds similar in structure to the applicants and even those differing only slightly'in the nature of the benzene ring substituents were tested and showed distinctly less activity than the applicants ingredients.

The following examples are given to illustrate this invention, and include both the preparation of the reaction product of this invention and Y test results on its usefor the indicated purposes:

EXAMPLE 1 01tho-thorg toluene A three way fiask 'equipped with a stirrer, a

return condenser, athermorneter and a dropping funnel, was charged with 80 gms. (2 moles) of sodium hydroxide, 890 hill of water and 216 gms.

(2 moles) of ortho cresol. The dropping funnel was charged with 308 gms. (Qmoles) of diethyl I I reactorwith stirring; and suihcient cooling to keep the-temperature below 25 C. All the diethyl sulfate. The mixture was cooled to 17 *C. whereupon the diethyl sulfate was added slowly to the sulfate was added over a period of about 20 minutes. Stirring was continued for l% hours, during-which ltime. the; temperature rose to 40 0.

tion with respect to the ethoxy group. A similar At this 3393111125 m1; bf 25% sodium hydroxide was added and the mixture was refluxed with stirring for three and one-half hours. The mixture was then cooleol and extracted with diethyl ether. The

ether extracts were combined, washed, and dried over sodium sulfate; On removal of the ether on the steam bath 198 gms. of a red oil'was obred oil. This too Was discarded.

fraction, the ortho-ethoxy toluene,

Final product The trichloro-derivative was prepared as follows:

A 3-way flask equipped with a stirrer, a return condenser, a thermometer and a dropping funnel was charged with 40.8 gms. (0.3 mole) of the ethoxy toluene described above, 24.8 gms. chloral hydrate, and 17 cc. of glacial acetic acid. The dropping funnel was charged with 51 cc. of concentrated sulfuric acid. The latter was then added to the reactor slowly over a period of 22 minutes. Sufficient cooling was employed to keep the reaction temperature below 35 C. during the addition of the acid.

When all the sulfuric acid had been added, the mixture was stirred for one hour at room temperature. At this point the product was poured into ice and water and was extracted with ether. The extract was washed with water and dried over sodium sulfate. The solvent was finally removed under reduced pressure at 40 C. The residue consisted of 55.7 gms. of yellow oil. The latter was evaluated as an insecticide without any further purification.

Chloral can be employed instead of chloral hydrate to obtain the same reaction products.

EXAMPLE 2 The products of this invention were tested for parasiticidal activity. The values given in column I of the following table represent the percentage mortality of the test insects after 96 hours following a two-minute immersion in an 0.25% aqueous solution or suspension of the test product.

The results in column II are given as percent mortality of the test insect after 96 hours following bloodstream injection of 0.002 cc. of a solution of the test product.

The figures in column HI list the results obtained on the Nelson Drop Test for house-fly toxicity. At full dosage, D, 5 mg. of test material/gm. body weight is placed in the flys body (0.002 cc. of a 5% solution per fly). Standards: 0.01 mg. DDT/gm. gives 65% kill (0.002 cc. of a 0.01% solution per fly.). 0.038 mg. pyrethrin/ gm. gives 40% kill (0.002 cc. of an 0.038% solution per fiy.).

Not all tests were performed on each product. The blank spaces indicate that that particulartest was not performed.

4 The product of this invention is indicated by Formula I above, and an analogous product by Formula II above. Both of these formulae are to be understood, of course, to constitute mix- 5 tures primarily of isomers with each of the indicated benzene ring substituents occurring in the para position as discussed above, and the other substituent occurring ortho thereto.

It should be noted from the results obtained 10 that the reaction product of this invention was many times superior to the analogous product indicated by II, about as good as DDT in activity and superior to pyrethrin on the Nelson Drop test.

15 EXAMPLE 3 The products of this invention were tested for housefly toxicity and knockdown strength on the Peet Grady test. The general test is fully described in the 1940 Blue Book, published by the publisher of Soap and Sanitary Chemicals periodical, on pages 193 to 197, as the large group method. Briefly, the test as practiced consists of releasing 100 to 150 flies in an air-conditioned case 6x6x6 feet and syraying them with 6 ml. of insecticide. After exposure the number of flies which are incapacitated or knocked down is noted and all flies transferred to a cage and allowed to recuperate in fresh air for 24 hours, when the dead flies are counted. The results 1 The fact that the products of this invention exhibit superior knockdown characteristics than the test insecticide should be particularly noted.

This is especially surprising in view of the well known inadequate knockdown strength of DDT' 5 and other related compounds.

By virtue of its solubility in the chloro-fluoro- Column II.Blood' Column I.-Contact stream Insecticidal Inse iticidalt%t1i1vity, activity, lzercent Killercen 1 mp one a amerwana (American Roach) %%Z' Toxicity Com ound I p Blatclla O melpeltus germamca cocratus Female Mal e5 fi (German (Milk Weed e 1 Roach) Bug) A B A B I. ClsCCH 75 100 100 100 D/5-100 D/lOO-IOO CH: D/200l00 D/500- CaHn II. ClaCCH E 5 40 D/1-5 III. DDT 100 100 100 100 D/100 100 D/500-65 D/1000-5O IV. Pyrethrin D/1324o methanes Freons, i. e. CClsF, CC12F2, CClFs, CHClzF etc., the reaction product from the condensation reaction between chloral hydrate and o-ethoxy toluene is adapted for use in aerosol compositions for space spray and fumigation applications. When put up in this form it can be dispensed in the conventional pressure containers known in the art. The active ingredient is present in an amount of about 1 to 5 wt. percent, and preferably 2 to 4 wt. percent.

For certain insecticidal purposes it is desirable to incorporate mineral spray oils in the aerosol formulations. These relatively non-volatile oils are added to the compositions indicated in the preceding paragraph up to a weight percent concentration of which represents the combined figure for the mineral spray oil and active insecticide.

The preferred mineral spray oils are the petroleum white oils or lubricating oil fractions such as medium or light lubricating oils, transformer oil, machine oil, deodorized kerosene, etc. The preferred mineral spray oil utilized in the aerosols is a sulfuric acid treated odorless kerosene.

The sulfuric acid-treated kerosene which may be utilized in the aerosols of this invention is also known as Bayol D and deodorized kerosene. Its preparation, i. e., by treating kerosene with fuming or concentrated sulfuric acid, is well known in the art. This acid treated kerosene has a specific gravity in the range of 0775-0825, a boiling point predominantly in the range of 400-505 F., and is substantially free of aromatics, i. e. contains only a trace. A typical inspection is as follows:

Per cent aromatics Trace A typical three-component formulation is thus as follows:

2-4 wt. per cent of the reaction product from the condensation reaction between chloral hydrate and o-ethoxy toluene.

2-11 wt. per cent sulfuric acid treated kerosene.

Freon q. s. (ad 100).

It is particularly preferred to utilize mixtures of Freons such as trichloro -mono -fluoromethane, and dichloro-di-fluoromethane.

It is to be understood that the invention is not limited to the specific examples which have been offered merely as illustrations, and that modifications may be made without departing from the spirit of the invention.

What is claimed is:

1. An insecticidal composition of superior knockdown characteristics consisting of a homogeneous liquid solution of a compound selected from the group consisting of 1,1,1,-trichloro- 2,2-(4A' diethoxy 3,3 dimethyldiphenyD- ethane and 1,1,1-trichloro-,2,2-(3,3-diethoxy 4, 4'-dimethyldiphenyl)-ethane in a chlorofluoromethane.

2. A composition as in claim 1, in which the chlorofluoromethane is di chloro di fluoromethane and the reaction product is present in an amount of from 2 to 4 weight per cent.

3. An insecticidal composition of superior knockdown characteristics consisting of a compound selected from the group consisting of 1,1,1- trichloro 2,2 -(4, l'- diethoxy 3,3- dimethyldiphenyl) ethane and 1,1,1 -trichloro-,2,2-(3,3- diethoxy-4,4'-dimethyldiphenyl)-ethane, a chloro-fluoromethane and a mineral spray oil.

4. A composition as in claim 3, in which the mineral spray oil is a sulfuric acid treated kerosene, said acid treated kerosene having a specific gravity in the range of 0.775 to 0.825, a boiling point predominantly in the range of 400 to 505 F., and being substantially free of aromatics.

5. An insecticidal composition of superior knockdown characteristics consisting of a compound selected from the group consisting of 1,1,1- trichloro-,2,2-(4,4' diethoxy 3,3 dimethyldiphenyl) ethane and 1,1,1 trichloro-,2,2-(3,3'- diethoxy 4,4 dimethyldiphenyl) ethane, trichloro-mono-fiuoromethane, di-chloro-di-fluoromethane, and a sulfuric acid treated kerosene, said acid treated kerosene having a specific gravity in the range of 0.775 to 0.825, a boiling point predominantly in the range of 400 to 505 F. and being substantially free of aromatics.

LOUIS A. MIKESKA.

References Cited in the file of this patent UNITED STATES PATENTS Name Date Goodhue et a1 June 8, 1943 OTHER REFERENCES Number 

1. AN INSECTICIDAL COMPOSITION OF SUPERIOR KNOCKDOWN CHARACTERISTICS CONSISTING OF A HOMOGENEOUS LIQUID SOLUTION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF 1,1,1,-TRICHLORO2,2-(4,4'' -DIETHOXY -3,3'' -DIMETHYLDIPHENYL)ETHANE AND 1,1,1,-TRICHLORO-2,2-(3,3''-DIETHOXY-4, 4''-DIMETHYLDIPHENYL)-ETHANE IN A CHLOROFLUOROMETHANE. 